Silicon nitride ceramics

ABSTRACT

Shaped ceramic objects of silicon nitride are protected from oxidation by a coating comprising silica and boric oxide. The coating may be formed by heating a shaped mixture of silicon nitride and boron nitride in air to convert part to silica and boric oxide and causing a silica/boric oxide glass to flux and protect the object from further oxidation. The boron may be incorporated during oxidation but is preferably added to the silicon before nitriding.

United States Patent 1191 Henney et al.

[ 1 May 21, 1974 SILICON NITRIDE CERAMICS 3,222,438 12/1965 Parr et a1... 106/55 3,394,026 7/1968 P t 1.. 117 169 R [75] Inventors: John Heme! Abmgdon? 3,226,194 12/1965 117/106 R James Wllllam Samuel Jones, 3,460,987 8/1969 McMillan et al. 117/219 Blewbury, both of England 3,428,466 2/1969 Wolf et a1. 106/39 R 2,844,637 7/1958 Bore] et a1. 106/52 [73] Assgnee' Umted .Kmgdom Amm'c Energy 3,238,085 3 1966 Hayami et a1 106/39 Authmty London England 2,618,565 11/1952 Nicholson 106/44 [22] Filed: Oct. 15 197 2,731,359 l/1956 Nicholson 1l7/DlG. 12

[ PP N05 189,583 4 Primary Examiner-Douglas J. Drummond Assistant Examiner-M. G. Wityshyn 3 Foreign Application priority Data' Attorney, Agent, or Firm-Larson, Taylor and Hinds O t. 20, 1970 G tB 't" 49855 70 c rea r1 am [57] ABSTRACT [52] US. Cl 117/106, 1 17/ 125, 106/69, Shaped ceramic objects of silicon nitride are protected Y 117/1310. 10, 117/D1G. 12 fr0m 0xidation by a coating comprising silica and [51] Int. Cl C04b 35/58 boric oxide. The coating may be formed by heating a [58] Field of Search 106/55, 39 R, 39, 12, 52, shaped mixture of silicon nitride and boron nitride in 106/44, 55, 69; 1 17/219, 229, 106, 123, 125, air to convert part to silica and boric oxide and caus- 169, DIG! 10, DIG. 12, 215 ing a silica/boric oxide glass to flux and protect the object from further oxidation. The boron may be in- [56] References Cited corporatedduring oxidation but is preferably added to UNITED STATES the silicon before nitriding. 3,468,992 9/1969 Lubatti 81. 211...; 106/44 x 8 Claims, 1 Drawing Figure 1m! fab/22w? 32m; aadanSW 31254. 2 2mm 51' 60/8 m 015 AWr/l/ig I ode/5on5 0 fabr/m/e m g 5 fabr/z'afe 3/ 4 5/ w 5/ A/ 3 2 3% 8 3% 341 i Z; f y 4 Bar% my 7 +5 w vb Ft'f .a/a'f pan/d 04 2 0 WW 4/ abjea/ 5709M fabr/Za/e 6 4/ 2 1 arm/7m 2/4 5; ages 2 5/4962 6/0925 fad/x7205- Pr/br /Mflt/ pie/E P0026? Pradw/ Fwd/m 4/1 4 D p 5 1 SILICON NITRIDE CERAMICS Silicon nitride is a useful ceramic material. It is strong and has a very low coefficient of thermal expansion. Its utility is however limited by the fact that it is liable to oxidation at elevated temperatures in air. We believe that oxygen reacts with surface silicon nitride (Si N with the formation of crystalline SiO mainly as Cristo balite which partially protects the remaining Si N from the atmosphere. Unfortunately, Cristobalite undergoes a phase change at about 230C. which is accompanied by a substantial volume change and causes cracking of the protective layer, with a consequent loss of strength so leaving the Si N once again open to oxidative attack from the atmosphere.

This invention relates to Si N ceramics, and to methods of making them, in which the .protective layer is modified to mitigate-or avoid the above disadvantage.

In one aspect the present invention provides a ceramic shaped object comprising Si N, and possibly BN protected from oxidation by a coating comprising SiO and B 7 In another aspect, the present invention provides a method of making the ceramic shaped object defined above, which-method comprises oxidizing silicon nitride (Si N under conditions to convert a part thereof to SiO boron being either provided in the material prior to oxidation or added to the material during oxidation, and heating the object so as to cause a SiO /B O glass to flux and protect the object from further oxidation. I

The silicon nitride will generally be made by nitriding silicon metal. It is preferred to add the boron, either as the element or as BN to Si metal powder, because more homogeneous mixtures of the nitrides are obtained in this way.

It is a further feature of this invention that one or more other materials, particularly Fe, Mg, Al, A1 0 MgO, CaO, BaO, ZnO or ZrO may be added to the silicon nitride, or more preferably to the silicon prior to nitriding, in an amount of up to 10 percent by weight on the weight of the final product. It is believed that CaO and BaO have the effect of suppressing the volatilisation of B 0 It is believed that the listed materials can have the effect-of crystallising what would otherwise normally be a SiO /B O glass. Provided that the crystalline material does not'undergo a phase and volume change on cooling (this is the disadvantage of pure SiO this modification can have the effect of improving the high temperature properties of the ceramic. However, it is important that the coefficient of thermal expansion of the second phase must be a reasonable match for the Si N, (2.5 X 10' /C.) if the body is to retain a high strength. The thermal expansion of SiO itself is very low (apart from the sudden volume change at 230C.) but is substantially increased by small addition of most other glass-making additives. B 0 is peculiar in that additions do not increase, and may even decrease, the thermal expansion of SiO The SiO /B 0 coating should preferably not have a coefficient of thermal expansion above 3 X l0 /C.

The above overall definitions cover a number of products which may be made by various methods according to the invention. These will now be described in turn. Reference is directed to the accompanying drawing, which is a diagram showing the various steps that can be taken. At the bottom of the diagram are five products, one of which is-conventional and contains no boron, and four of which are letteredA, B, C and D and are within the scope of this invention. Basically, all the preparative methods described start from silicon metal powder, and involve two main steps, that is to say, nitriding and oxidation, with boron being added to the silicon in some form before or during the nitriding or the oxidation stages. Product C is the preferred product.

All the preparative methods involve fabricating powders into shaped objects. Fabrication may be achieved by normal powder ceramic fabrication processes, which are well known in the art; The method of fabrication of powder into shaped objects is not relevant to this invention, and will not be further describedherein.

(1,410C.), usually at l,300C. to 1,350C. for long enough to form a Si N matrix. The temperature is then further raised to, for example 1,450C; to complete the nitriding. Unchanged Si may melt at this higher temperature, but the Si N matrix keeps the object rigid until nitriding is complete. If the ceramic product is, to be of high strength, the nitriding step must be taken to substantial completion.

The heating time for this nitriding step depends on the size of the object. Large objects may require to be heated, for example, for 10 hours at 1,350C. followed by 24 hours at 1,450C. Smaller objects, for instance cylindrical pellets 1cm. in diameter by /2 cm: long, may be completely nitrided after 2-hours at 1,350C. followed by 10 hours at 1,450C.

These long times and high temperatures are expensive on both power and equipment. The nitriding step in fact represents a major part of the cost of making Si N ceramic articles. It is therefore preferable that nitriding should be carried out on a material in finely divided form, e.g. powder or pellets. It is a disadvantage of product A (and of product B see below) that its manufacture requires the nitriding of large shaped obects.

After nitriding, the shaped object consists of a 3- a glass that fluxes to form a continuous gas-- impermeable layer over the entire object; this glass having the advantage over Cristobalite that it does not crack as a result of phase changes during cooling.

At oxidation temperaturesbelow l,l50C., the glass may not flux adequately to give an impermeable layer.

At oxidation temperatures above 1,350C., the B 0 may be too volatile to condense with the SiO,. Oxidation may conveniently be effected in a closed vessel in which boron or B 0 has been placed with the shaped up to percent, e.g. 1 percent to 5 percent of the weight of the object and will contain from 1 percent to percent by weight of B 0 Product A, prepared as described above, is a shaped object consisting essentially of a matrix of Si N and a gas-impermeable surface layer comprising SiO and B 0 EXAMPLE 1 A specimen of Si N (density 2.2 g/cc) was heated in a closed alumina crucible with B 0 vapour for 1 hour at l,350C. On cooling no crystalline SiO was detected on the specimen surface and the Modulus of Rupture was 15,500 p.s.i.

A similar specimen heated without B 0 vapour pres ent had a surface layer of a Cristobalite on cooling and an MOR of 7,700 p.s.i.

Product B. I

The preparation of product B is similar to that described for product A, except that the boron is added to the Si before the nitriding step, rather than during oxidation.

Tosilicon metal powder is added boron, either as the element or as BN, preferably in a proportion of from 1 percent to 20 percent, e.g., 2 percent to 10 percent of boron by weight on the weight of the Si. The powdered mixture is fabricated into a shaped object, which is then the two oxides combining to form a glass. These reacnitrided. The nitriding step forms no part of this invention, and has already been discussed above in relation to product A. It is merely necessary to add that the presence of boron does not alter the nitriding conditions, and that elemental boron is nitrided along with the silicon. However, the heating rate to 1,100C. should not exceed 200C./h if no dimensional change is to occur.

After nitriding, the shaped object consists of a threedimensional matrix of essentially B Si N, in which there is incorporated a minor proportion of BN. This is then oxidised, conveniently in air,-preferably at a temperature of from l,150 to 1,350C. At temperatures of this order, it is believed that Si N and EN on the surface of the object are oxidised to SiO and B 0, respectively, to give a glass that fluxes to form a continuous gas-impermeable layer over the entire object; this glass having the advantage over Cristobalite that it does not crack as a result of phase changesduring cooling.

At oxidation temperatures below 1,150C., the glass may not flux adequately to give an impermeable layer.

At oxidation temperatures above 1,350C., B 0; is rather volatile. Generally, the oxide layer will constitute up to 5 percent, e.g. 1 percent to 5 percent, of the weight of the object.

Product B, prepared as described above, is a shaped object consisting essentially of a matrix of Si;N in which there is incorporated a minor proportion of BN, and a gas-impermeable surface layer comprising SiO,

' and B203.

boron by weight on the weight of the Si. This mixture is nitrided conveniently as a powder or in the form of pellets. The nitriding step forms nopart of this invention, and has already been discussed in relation to product A. The resulting mixture of Si N, and RN, if not already in powder form, will generally need to be powdered for further use. This mixture, containing up to 20 percent of boron by weight on the weight of the Si, is believed to be novel, and forms a subsidiary aspect of our invention. BN is somewhat soluble in Si N and tends to stabilise the B Si N phase.

As can be seen from the diagram, it is possible to proceed in either of two ways from this point. According to one alternative, the powdered Si NJBN mixture is fabricated into a shaped object which is then heat treated. Heat treatment is preferably carried out in two stages, the first stage in an oxidising atmosphere, conveniently air, below about 1,150C., e.g. at a temperature of from 900? to 1,150C., preferably 1,000 to 1,l0OC., and the second stage, optionally, but not necessarily, in an oxidising atmosphere, above about l,150C., e.g., at a temperature of from l,lC. to 1,400C., preferably 1,200C. to l,350C. The changes which occur during heat treatment are believed to be as follows. During the first stage, oxygen permeates the entire body and slowly oxidises Si N, to SiO, and EN to 8,0,,

tions continue throughout the first stage. The amount of glass formed is therefore determined by the length of time for which the object is held at'from 900 to ll50C. When the temperature is subsequently raised to from l,150 to 1,400C.,' the glass fluxes and forms a gas-impermeable coating round the remainingShN,

and EN, protecting them from further oxidation. lt is probable that some Si N, also dissolves'in the glass at the higher oxidation temperatures, and subsequently. precipitates out on cooling in the form of a threedimensional matrix.

The time for which the object is held at an elevated temperature during thev oxidation stageof heat treat ment depends on temperature chosen and on i the amount of glass (discussed below) which is desired in the product. Times of from l0 seconds at 1,150C. to 12 hours at 900C. arelikely tobe-appropriate. While it is preferred to hold the object at a temperature in the range 900 to 1 ,150C. for a definite length of time, before heating further, it may under somecircumstances be sufficient to simply heat the object up to a temperature in the range l,l50 to l,400C., the unavoidable heating time during which the object is at a temperature of from 900C. to l,l50C. constituting the oxidation stage of the heat treatment.

The holding time-for the second stage of the heat treatment should be sufficient to achieve equilibrium in the object resulting from fluxing of the SiO,/B,O glass and solution of the Si N therein. Preferred holding times range from A hour upwards, depending on the EXAMPLE 2 A 95:5 "/0 Si:B mixture was nitrated for 2h at 1,350C. and h at l,450C. to give. a product consisting essentially of ,3 Si -,N with a small amount of BN. This was ground to powder 300 mesh 8.5.5.) and cold compacted at 10,000 p.s.i. to form rectangular specimens 2.5 X 0.6 X 0.3 cm. These were heated in air as described below and had the average properties given in the Table.

Estimated Modulus of Firing Schedule Glass Content Density Porosity Rupture, p.s.i.

(1) Rise of temp.

20C/min. Held 2h at 30 /o 2.6 5 15000 18000 Ductile 1050C. and g/cc at 1050C. 2h at 1350C.

(2) Rise of temp.

' 30C/min.

Held 1h at 20 '/o 2.3 20 l3000 l4000 Ductile 1350C. g/cc at ll50C.

(3) Rise of temp.

15C/min. Held 1h at "/o 2.2 23 13000 14000 Ductile 1350C. g/cc at 1050C.

ature above about 1,150C., preferably l,150 to 1,400C., e.g. l,200 to 1,350C., to flux the glass and prevent further subsequent oxidation. It should be noted'that this second stage heating need not be in an oxidising atmosphere; indeed it may be preferable to use an inert atmosphere to prevent further oxidation.

Product C, prepared as described above, consists essentially of a mixture of B Si N and BN bonded throughout by means of a glass comprising SiO and B 0 in which the Si N probably forms a continuous matrix. The product has the interesting property of becoming ductile when the glass softens at elevated temperatures of the order of 1 ,100 to 1,300C., thus opening up possibilities of making further shapes by forging or hot-pressing processes, or of welding products. We have successfully welded products of this kind at temperatures of the order of 1,400C. using an oxyacetylene torch. This property of ductility also means that high temperature failure of a component (e.g. a turbine blade) in service is likely to be by distortion or creep, rather than by break-up, which may be advantageous.

Ductility of this product is a function of SiO /B O glass content. The proportion of glass to nitride in the product is not critical, in the sense that useful products are obtained with a wide range of glass contents, but is likely to be in the range of 50:50 to 5:95, e.g. 40:60 to 20:80, expressed by weight as (SiO /B O ):(Si N /BN).

The incorporation of a minor amount of one or more further materials, e.g. Fe, Mg, Al, A1 0 MgO, CaO, BaO, ZnO or ZrO in the product, as described above, can have the effect of increasing or decreasing the temperature at which ductility becomes apparent. For example, the addition of small amounts of MgO and A1 0 to the silicon metal powder before nitriding can increase the temperature at which ductility appears from about l,200 to about 1,400C.

Resistance to further oxidation was demonstrated by specimens from (2) which increased in weight by less than 1 percent on being heated in water saturated oxygen for l20h at 1,250C.

Resistance to thermal shock was demonstrated by specimens from (3) which underwent six cycles of rapid heating and cooling (1,000C/min.) in air between 50 and 800C. without any loss of strength.

A further six cycles in which the specimens were quenched in water lowered their modulus of rupture to about half its previous value.

Product D. Y

The first step in the preparation of product D is the conventional nitriding of silicon metal, conveniently in powder or pellet form. The nitriding step has already been discussed in relation to product A. The resulting Si N if not already in powder form, will generally need to be powdered for further use.

As can be seen from the diagram, it is possible to proceed in any one of three ways from this point. According to the first alternative, the Si N powder is fabricated into a shaped object. It may be mentioned that Si N powder is difficult to sinter alone, so that the shaped object at this stage has low strength and needs careful handling.

The shaped object is then oxidised in an oxidising atmosphere (conveniently air) containing B 0 The oxidising treatment is preferably the same as the two-stage treatment described in relation to product C. Apart from the fact that the B 0 permeates the shaped object with the oxygen, rather than being formed in situ by oxidation of BN, the changes which take place during the treatment are believed to be essentially the same. That is to say, in the first stage, Si N is slowly oxidised throughout the object to SiO which combines with 13 0 vapour to form a glass. 1n the second stage, the glass fluxes and forms a gas-impermeable coating around the remaining Si N A sqrs ins. .1 "the. seated altmat xt,th9.a& powder is sub ected to the oxidising stage of the twostage heat treatment described above in relation to product C, except that the oxidising atmosphere also contains B 0 The product is then cooled and ground. It is a mixture of Si N SiO and B 0 and constitutes another subsidiary aspect of our invention. This mixture is then fabricated into a shaped article which is subjected to the second stage of the heat treatment described above in relation to product C.

According to the third alternative, the Si N powder is mixed with boron, either as the element or in the form of B 0 The resulting mixture is subjected to the two-stage heat treatment described above in relation to product C. The powdered mixture may be fabricated into a shaped object either before the oxidation stage of the heat treatment or between the first and second stages as previously described' Product D, prepared as described above, consists essen tially of Si N bonded throughout by means of a glass comprising SiO and B 0 in which the Si3N probably forms a continuous matrix. The product is similar to product C, and in particular has the same property of ductility at elevated temperature.

We claim:

1. A ceramic shaped object consisting essentially of a matrix of Si N protected from oxidation by a gasimpermeable surface layer comprising SiO and B 0 wherein the surface layer constitutes from 1 percent to 5 percent of the weight of the article and contains from 1 percent to percent by weight of B 0 2. A ceramic shaped object as claimed in claim 1, comprising up to 10 percent of one or more of Fe, Mg, Al, A1 0 MgO, CaO, BaO, ZnO and ZrO;.

3. A ceramic shaped object consisting essentially of a matrix of Si N in which there is incorporated BN in an amount of from 1 percent to 20 percent of boron by weight on the weight of the silicon, protected from oxidation by a gas-impermeable surface layer comprising SiO, and B 0 wherein the surface layer constitutes from 1 percent to 5 percent of the weight of the article and contains from 1 percent to 20 percent by weight of 1 3- 4. A ceramic shaped object as claimed in claim 3, comprising up to 10 percent of one or more of Fe, Mg, Al, Al O MgO, CaO, BaO, ZnO and ZrO,.

5. A ceramic shaped object consisting essentially of a mixture of Si N, and EN protected from oxidation and bonded throughout by means of a glass comprising SiO and B 0 wherein a. the weight of boron is from 1 percent to 20 percent of the weight of the silicon, and

b. the weight ratio of (SiO /B O ):(Si,N /BN) is from 6. A ceramic shaped object as claimed in claim 5, comprising up to 10 percent of one or more of Fe, Mg, Al, A1 0 MgO, CaO, BaO, ZnO and zro,

7. A ceramic shaped object consisting essentially of Si N, protected from oxidation and bonded throughout by means of a glass comprising SiO and 8,0,, wherein comprising up to 10 percent of one or more of Fe, Mg,

Al, A1 0 MgO, CaO, BaO, ZnO and ZrO 

2. A ceramic shaped object as claimed in claim 1, comprising up to 10 percent of one or more of Fe, Mg, Al, Al2O3, MgO, CaO, BaO, ZnO and ZrO2.
 3. A ceramic shaped object consisting essentially of a matrix of Si3N4, in which there is incorporated BN in an amount of from 1 percent to 20 percent of boron by weight on the weight of the silicon, protected from oxidation by a gas-impermeable surface layer comprising SiO2 and B2O3, wherein the surface layer constitutes from 1 percent to 5 percent of the weight of the article and contains from 1 percent to 20 percent by weight of B2O3.
 4. A ceramic shaped object as claimed in claim 3, comprising up to 10 percent of one or more of Fe, Mg, Al, Al2O3, MgO, CaO, BaO, ZnO and ZrO2.
 5. A ceramic shaped object consisting essentially of a mixture of Si3N4 and BN protected from oxidation and bonded throughout by means of a glass comprising SiO2 and B2O3, wherein a. the weight of boron is from 1 percent to 20 percent of the weight of the silicon, and b. the weight ratio of (SiO2/B2O3):(Si3N4/BN) is from 50:50 to 5:95.
 6. A ceramic shaped object as claimed in claim 5, comprising up to 10 percent of one or more of Fe, Mg, Al, Al2O3, MgO, CaO, BaO, ZnO and ZrO2.
 7. A ceramic shaped object consisting essentially of Si3N4 protected from oxidation and bonded throughout by means of a glass comprising SiO2 and B2O3, wherein a. the weight ratio of (SiO2/B2O3):Si3N4 is from 50:50 to 5:95, and b. the said glass contains from 1 percent to 20 percent by weight of B2O3.
 8. A ceramic shaped object as claimed in claim 7, comprising up to 10 percent of one or more of Fe, Mg, Al, Al2O3, MgO, CaO, BaO, ZnO and ZrO2. 